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Theoretical study on thermal decomposition of azoisobutyronitrile in ground state

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Science china chemistry 2004年第5期47卷 373-380页

作者： SUN Chengke1,2. ZHAO Hongmei1 & LI Zonghe1 1. department of chemistry, Beijing {2. University, Beijing 100875, china 2. department of chemistry, qujing {2. college, qujing 655000, china 1. department of chemistry Beijing Normal University 100875 Beijing China 2. department of chemistry Qujing Normal College 655000 Qujing China

The thermal decomposition mechanisms of azoisobutyronitrile (AIBN) in the ground state have been investigated systematically. Based on the potential energy surfaces (PES) of various possible dissociation paths obtained using the semiempirical AM1 method with partial optimization, the density function theory B3LYP/6-311G* method was employed to optimize the geometric parameters of the reactants, the intermediates, the products and the transition states, which were further confirmed by the vibrational analysis. The obtained results show that the re- action process of the two-bond (three-body) simultaneous cleavage Me2.CN)C─ N=N─ C(CN)Me2. 2.e2.CN)C?+N2.is much more favorable than the reaction process of the two one- bond asynchronous cleavage Me2.CN)CN=N─C(CN)Me2.? Me2.CN)CN=N?+ Me2.CN)C?? Me2.CN)C?+ N2. It was suggested that the electron shrinking effect of double bond (─N=N─) in AIBN and the stabilities of the Me2.CN)C?radical as well as N2.molecule are main factors of leading to the reaction proceeding in the former pathway. The calculation results were consistent with all the experimental facts.

关键词： azoisobutyronitrile, radicals, thermal decomposition, density function theory (DFT).

Asymmetric radical allylation of β-keto esters with vinyl cyclopropanes by dual photoredox/nickel catalysis

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Science china chemistry 2024年第11期67卷 3807-3816页

作者： Wen-Yuan qu Xue-Song Zhou Wen-Jing Xiao Jia-Rong Chen Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction Ministry of EducationCollege of Chemistry Central China Normal University Wuhan Institute of Photochemistry and Technology Key Laboratory of Organo-Pharmaceutical chemistry of Jiangxi Province Gannan Normal University

Radical-involved allylation reactions have emerged as a powerful platform for construction of carbon-carbon and carbonheteroatom bonds, facilitating the strategic incorporation of diverse allyl moieties. Nevertheless, this burgeoning field still faces ongoing challenges, including limitations of radical precursors and coupling partners, and difficulties in achieving enantiocontrol. Herein, we report for the first time a highly enantioselective radical allylation involving β-keto esters with vinyl cyclopropanes utilizing a synergistic dual photoredox/nickel catalysis under visible light irradiation. The mild and redox-neutral catalytic protocol demonstrates an extensive substrate compatibility and good functional tolerance, providing access to enantioenriched β-keto esters featuring quaternary α-stereocenter with good yields and high enantioselectivities. Preliminary mechanistic studies have uncovered that the success of the reaction hinges on the dual roles of nickel catalyst, including in situ formation of photoredox sensitive substrate/Ni complex and the ensuing asymmetric radical addition step.

关键词： asymmetric allylation photoredox catalysis radical addition nickel catalysis β-keto esters vinyl cyclopropanes

Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine

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Science china chemistry 2006年第4期49卷 296-307页

作者： LI Ming1, ZHEng Wenxu2.& TIAN Anmin2.1. department of chemistry, Southwest-{2. normal University, Chongqing 400715, china 2. department of chemistry, Sichuan University, Chengdu 610064, china 1. department of chemistry Southwest-China Normal University Chongqing 400715 China 2. department of chemistry Sichuan University Chengdu 610064 China

The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this re- action are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.

关键词： keto oxime ether, oxazaborolidine, enantioselective reduction, DFT.

Enhanced red luminescence of Ca_(3)Si_(2.x)M_(x)O_(7):Eu^(3+)(M=Al,P)phosphors via partial substitution of Si^(4+) for applications in white light-emitting diodes

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Rare Metals 2024年第2期43卷 736-748页

作者： Yu-Hao Ma Xi Gao Wen-Tao Zhang Zhen-Rui Yang Zhou Zhao Chen qu college of Materials and chemistry and Chemical Engineering Chengdu University of TechnologyChengdu610059China State Key Laboratory of Geohazard Prevention and Geoenvironment Protection Chengdu University of TechnologyChengdu610059China International Advanced Energy Science Research and Education Center Graduate School of Energy ScienceKyoto UniversityYoshida-HonmachiKyoto606-8501Japan

A red-emitting phosphor Ca_(2.91)Si_(2.O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2.x)M_(x)O_(7):0.09Eu^(3+) phosphors were *** X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2.O_(7) remained the same after the introduction of Al^(3+) and P^(5+) *** characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2.x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2.and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) *** the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2.O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42.fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 2.0℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal ***,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity *** summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2.O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.

关键词： Ca_(3)Si_(2.O_(7) Red-emitting phosphor Structure substitution Luminescence enhancement Crystal-field effect White light-emitting diode

Molecular modeling and spectroscopic studies on the binding of guaiacol to human immunoglobulin

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Science china chemistry 2006年第6期49卷 550-559页

作者： HE Wenying1,2. YAO Xiaojun1, LIU Pengjun2. GAO Zhenxia2.& HU Zhide1 1. department of chemistry, Lanzhou University, Lanzhou 730000,{2. 2. department of chemistry, Hainan normal University, Hainan 571158,{2. 1. department of chemistry Lanzhou University Lanzhou 730000 China 2. department of chemistry Hainan Normal University Hainan 571158 China

The fluorogenic property of guaiacol was exploited for the first time to analyze the interaction with target protein as a probe by molecular modeling, fluorescence, circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. Molecular docking was performed to reveal the possible binding mode or mechanism and suggested that guaiacol can strongly bind to human immu- noglobulin (HIgG). It is considered that guaiacol binds to HIgG mainly by a hydrophobic interaction and there are two hydrogen bond interactions between the drug and the residues LEU 80 and ASP 65, which is in good agreement with the results from the experimental thermodynamic parameters (the enthalpy change △H0 and the entropy change △S0 were calculated to be 65.55 kJ·mol-1 and 132.95 J·mol-1·K-1 according to the Vant’ Hoff equation). Data obtained by the fluorescence spectroscopy indicated that binding of guaiacol with HIgG leads to dramatic enhancement in the fluorescence emission intensity along with significant occurrence of efficient Frster resonance energy transfer (FRET) from the residue of HIgG to the protein bound guaiacol. From the low value of fluorescence anisotropy (r = 0.06), it is argued that the probe molecule is located in the motionally unrestricted environment of the protein. The alterations of protein’s secondary structure in the presence of guaiacol in aqueous solution were quantitatively calculated by the evidences from FT-IR and CD spectroscopes.

关键词： guaiacol, human immunoglobulin, molecular modeling, fluorescence enhancement, Fourier transform infrared (FT-IR) spectroscopy, circular dichroism (CD).

Fuzzy controllers based on some fuzzy implication operators and their response functions

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Progress in Natural Science:Materials International 2004年第1期14卷 16-21页

作者： LI Hongxing 1*, YOU Fei 1 and PEng Jiayin 2.1. department of Mathematics, Beijing normal University, Beijing 100875,{2. 2. department of Mathematics, Neijiang Teacher's college, Neijiang 641112.{2.) Beijing normal Univ Dept Math Beijing 100875 Peoples R China

The fuzzy controllers constructed by 2. fuzzy implication operators based on CRI algorithm and their response functions are discussed. The conclusions show that the fuzzy controllers constructed by 9 fuzzy implication operators are universal approximators to continuous functions and can be used in practical fuzzy control systems. And these 9 fuzzy implication operators except for Einstein operator intersection are all the adjoint pairs of some fuzzy implication operators. Besides, there are 3 other fuzzy controllers formed by fuzzy implication operators being regarded approximately as fitted functions.

关键词： fuzzy implication operators CRI algorithm fuzzy controllers response functions universal approximators

Approach to synthesis of novel chiral 3-chloro-2.5H)- furanone and its application in asymmetric reactions

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Chinese Science Bulletin 2000年第8期45卷 711-716页

作者： HUAng Hui & CHEN Qinghua1. department of chemistry, Tonghua Teacher’s {2., Tonghua 134002. china 2. department of chemistry, Beijing normal University, Beijing 100875, china department of chemistry Tonghua Teacher’s College Tonghua China department of chemistry Beijing Normal University Beijing China

The synthetic method of the novel chiral synthon, 5-/-menthyloxy-3-chloro-2.(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucieophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR, H NMR,13 C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(/-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2.3i(4’-/-menthyloxy-5’-/-menthyloxy- butyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex

关键词： new chiral synthon. 5-l-menthyloxy-3-chloro-2.(5H)-furanone absolute configuration spiro-cyclopropane derivative containing multiple chiral centers.

Adsorption and corrosion inhibition behavior of imidazole on cobalt electrodes studied by SERS and electrochemical methods

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Science china chemistry 2005年第6期48卷 497-503页

作者： GU Wei1, LIU Guokun2. REN Bin2. WU Deyin2. GU Renao1 & TIAN Zhongqun2.1. department of chemistry, {2. of chemistry and Chemical Engineering, Suzhou University, Suzhou 2.5006, china 2. State Key Laboratory for Physical chemistry of Solid Surfaces and department of chemistry, {2. of chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, china 1. department of chemistry College of Chemistry and Chemical Engineering Suzhou University 215006 Suzhou China 2. State Key Laboratory for Physical chemistry of Solid Surfaces and department of chemistry College of Chemistry and Chemical Engineering Xiamen University 361005 Xiamen China

The interaction of imidazole with Co electrodes in an electrochemical system was studied by surface-enhanced Raman scattering (SERS) and electrochemical methods. The SER spectra of Co in an imidazole solution as a function of the applied potential were analyzed and the assignment of the Raman bands was made. It was found that there were three kinds of sur-face species on the Co surface in different potential regions and they were interchangeable de-pending on the potential. In a relatively negative potential region (?1.2.to ?0.9 V), imidazole was adsorbed on the surface and its orientation might change from a vertical configuration via the N-end of the pyridine ring to a tilted configuration via the C2.N3 double bond. In a more positive potential region (?0.8 to ?0.7 V), the SERS signal from the adsorbed imidazole weakened and finally disappeared, meanwhile the signal from the Co and imidazole complex strengthened gradually. At the open circuit potential (?0.6 V), we detected very strong bands from the Co ox-ides. By comparing the Tafel curves of the Co electrode in the solution without and with imidazole, we found that imidazole has a marked effect on the corrosion inhibition of the Co electrode. This result demonstrates that we may be able to reveal the complicated interaction of surface species with metal surface at the molecular level by combining the SERS and electrochemical methods.

关键词： cobalt, imidazole, inhibition, surface-enhanced Raman spectroscopy, Tafel plot.

A Selenium Atom Involved Covalent Organic Framework for Window Ledge Photocatalytic Oxidation of Sulfides

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Chinese Journal of chemistry 2024年第17期42卷 1960-1966页

作者： Fan Yang Xia Li Hong-Yan qu Jing-Lan Kan Yuan Guo Yu-Bin Dong college of chemistry Chemical Engineering and Materials ScienceCollaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of ShandongKey Laboratory of Molecular and Nano ProbesMinistry of EducationShandong Normal UniversityJinanShandong250014China School of Light Industry and Engineering Qilu University of Technology(Shandong Academy of Sciences)JinanShandong 250353China

Covalent organic frameworks(coFs)driven photocatalytic organic transformations especially photooxidation reactions have become a fertile topic and attracted numerous research *** the charge generation and transport process is the key factor for achieving high catalytic *** one of the most effective strategies,the introduction of"heavy atoms"into the long-range ordered conjugated backbones can effectively facilitate the intersystem crossing(isc)process and hence improve the generation of active oxygens,which is beneficial for the *** this work,we designed and synthesized a benzoselenadiazole based covalent organic framework(COF)material,BSe-COF with heavy atom of selenium(Se),and a benzothiadiazole based BT-COF with isomorphic backbone for comparison.

关键词： Covalent organic framework Benzoselenadiazole Density functional theory Heavy atom Photocatalysis Photooxidation Singletoxygen Window ledge reaction